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Electronic structure and photoelectron spectra of bispentalene complexes of thorium and uranium

journal contribution
posted on 2023-06-08, 00:24 authored by Geoff Cloke, JC Green, CN Jardine
The preparation of [U{¿8-C8H4(1,4-SiiPr 3)2}2] is reported. The binding of the pentalene ligand in an ¿8 mode is examined by density functional calculations and photoelectron spectroscopy. Geometry optimization of [M(¿8-C8H6)2], M = Th with D2d and D2 symmetry constraints, gives structures in good agreement with the X-ray structure found for [Th{¿8-C8H4(1,4-SiiPr 3)2}2); in particular the folded nature of the ligand is well reproduced by the calculation. Examination of the barrier to relative rotation of the two ligands only showed a significant energy rise when the two rings were eclipsed. Geometry optimization for M = U, assuming D2d symmetry and a triplet state, gave a structure similar to the Th compound but with shorter metal-carbon bond lengths. The two U f electrons were constrained to occupy degenerate orbitals of e symmetry. He I and He II spectra of [M{¿8-C8H4(1,4-SiiPr 3)2}2], M = Th and U, are presented and assigned with the aid of density functional calculations. The principal binding is by d bonds between the upper occupied p orbitals of the pentalene dianion and the actinide d and f orbitals of appropriate symmetry.

History

Publication status

  • Published

Journal

Organometallics

ISSN

02767333

Issue

6

Volume

18

Department affiliated with

  • Chemistry Publications

Full text available

  • No

Peer reviewed?

  • Yes

Legacy Posted Date

2012-02-06

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